ZAHARIDE

DENUMIRE: compuyi carbonilici polihidroxilici.

-ZAHARIDE (sau zaharuri): zaharoza C
12
(H
2
O)
11
-HIDRATI DE CARBON, formule moleculare C
n
(H
2
O)
n
,
glucoza C
6
(H
2
O)
6
)
-GLUCIDE denumire propus n 1927 de Comisia Interna(ional
pentru Nomenclatur (glucos dulce).
CLASIFICARE:
a) a) Oze (monozaharide): compuyi carbonilici polihidroxilici
b) b) Ozide:
b.1) Holozide
-oligozaharide (zaharide care contin ntre 2 si 6 resturi de monozaharide
unite ntre ele prin legturi glicozidice)
-polizaharide (zaharide Iormate dintr-un numr mai mare de 6 resturi de
monozaharide unite ntre ele prin legturi glicozidice).
b.2) Heterozidele con(in pe lng componenta glucidic yi o
component neglucidic denumit ,glicon.
MONOZAHARIDE(OZE)
ompusi carbonilici polihidroxilici.
CLASIFICARE
a) Dup numrul atomilor de carbon componenti ai moleculei:
trioze (

),
tetroze (

),
pentoze (

),
hexoze (
6
), etc.
b) Dup natura grupei carbonil:
aldoze (continnd o grupare aldehidic),
cetoze (continnd o grupare cetonic).
CH
2
OH
C O
CH
2
OH
CH
2
OH
C O
C OH H
CH
2
OH
CH
2
OH
C O
C OH H
C OH H
CH
2
OH
1,3-dihidroxiacetona
cetotrioza
1,3,4-trihidroxibutanona
cetotetroza
cetopentoza
CH
2
OH
C O
C OH H
C OH H
C
cetohexoza

CH
2
OH
CHO
C OH H
CH
2
OH
CHO
C OH H
C OH H
CH
2
OH
CHO
C OH H
C OH H
C OH H
CH
2
OH
CHO
C OH H
C OH H
C OH H
C OH H
CH
2
OH 2,3-dihidroxipropanal
aldotrioza
2,3,4-trihidroxibutanal
aldotetroza
aldopentoza aldohexoza
STRUCTURAmonozaharidelor

ldehida
D()-glicerica
ldehida
L(-)-glicerica
ldehida
D()-glicerica
ldehida
L(-)-glicerica
CHO
OH
CH
2
OH
H
HO H
CHO
OH
CH
2
OH
H HO
H
CHO
OH
CH
2
OH
H
HO
H
CHO
OH
CH
2
OH
H
HO
H
(+) racemic
forma 07974
L(+)-treoza
D(-)-treoza D(-)-eritoza L(+)-eritoza
(+) racemic
forma 9704
enantiomeri enantiomeri
diastereoizomeri
2
n
stereoizomeri
onIiguratie absoluta R S
CHO
C OH H
CH
2
OH
CHO
C OH H
C OH H
CH
2
OH
CHO
C OH H
C OH H
C OH H
CH
2
OH
CHO
C OH H
C OH H
C OH H
C OH H
CH
2
OH
CHO
C HO H
C OH H
CH
2
OH
CHO
C HO H
C OH H
C OH H
CH
2
OH
CHO
C OH H
C HO H
C OH H
CH
2
OH
CHO
C HO H
C HO H
C OH H
CH
2
OH
CHO
C HO H
C OH H
C OH H
C OH H
CH
2
OH
CHO
C OH H
C HO H
C OH H
C OH H
CH
2
OH
CHO
C HO H
C HO H
C OH H
C OH H
CH
2
OH
CHO
C OH H
C OH H
C HO H
C OH H
CH
2
OH
CHO
C HO H
C OH H
C HO H
C OH H
CH
2
OH
CHO
C OH H
C HO H
C HO H
C OH H
CH
2
OH
CHO
C HO H
C HO H
C HO H
C OH H
CH
2
OH
D(+)-glicerinaldehida
D(-)-eritroza D(-)-treoza
D(-)-riboza
D(-)-arabinoza
D(+)-xiloza D(-)-lixoza
D(+)-aloza D(+)-altroza
D(+)-glucoza D(+)-manoza
D(+)-guloza D(+)-idoza
D(+)-galactoza D(+)-taloza
Structuri ciclice
rezultate prin reactia de semiacetalizare intramolecular caracteristic
compusilor , o-hidroxicarbonilici
Tautomeria oxo-ciclic (inel-caten)
OH
CH=O
H
2
C
H
2
C
C
H
2
O
CH
H
2
C
H
2
C
C
H
2
OH
H
2
C
H
2
C CH
2
OH
C=O H
2
C
H
2
C
H
2
C CH
2
O
C H
2
C
OH
CH
3
H
3
C
-hidroxialdehida
4-hidroxibutanal
12%
-lactona
2-hidroxitetrahidrofuran
88%
0-hidroxihexan-2-ona
0-hidroxi-2-metil-
tetrahidropiran
CHO
C OH H
C HO H
C OH H
C OH H
CH
2
OH
C
C OH H
C HO H
C OH H
C H
CH
2
OH
H
OH
O
C
C OH H
C HO H
C OH H
C H
CH
2
OH
H
HO
O
C
C OH H
C HO H
C H
C H
CH
2
OH
H OH
O
OH
C
C OH H
C HO H
C H
C H
CH
2
OH
H
HO
O
OH
formule de proiectie Fischer ale D(+)-glucozei
formula aciclica
(carbonilica)
-glucopiranoza .glucopiranoza
-glucofuranoza
.glucofuranoza
CH
2
OH
C O
C HO H
C OH H
C OH H
CH
2
OH
C
C HO
H
C OH H
C OH H
C H
HO-H
2
C
OH
O
C
C HO H
C OH H
C OH H
H
2
C
CH
2
OH
HO
O
C
C HO H
C OH
H
C H
H
2
C
HO-H
2
C OH
O
OH
C
C HO
H
C OH H
C H
H
2
C
HO
CH
2
OH
O
OH
formule de proiectie Fischer ale D-fructozei
formula aciclica
(carbonilica)
-fructopiranoza .fructopiranoza
-fructofuranoza
.fructofuranoza
H
OH
H
H
COH
H
OH
OH
H
O
O
H
OH
H
OH
H
OH H
OH
CH
2
OH
O
H
OH
OH
H
H
OH H
OH
CH
2
OH
H
CH
2
OH
OH
H H
COH
H
OH
OH
H
O
CH
2
OH
1
2 3
4
5
6
--D-glucopiranoza
1
2 3
4
5
6
.-D-glucopiranoza
--D-glucofuranoza
.-D-glucofuranoza
1
2 3
4
5
6
formule perspectivice Haworth
H
Iormulele conIormationale
O
OH
OH
HO
HO
HOH
2
C
O
OH
OH
OH
OH
CH
2
OH
--D-glucopiranoza

O
OH
OH
HO
HO
HOH
2
C
.-D-glucopiranoza
O
OH
OH
HO
HO
HOH
2
C
--D-glucopiranoza
Solutie apoasa 6 6
Efectul anomeric
O
O
OH
HO
HO
HOH
2
C
--D-glucopiranozida
O
O
OH
HO
HO
HOH
2
C
.-D-glucopiranozida
R
R
Denumirea ozelor (monozaharidelor)
-apartenenta la seria steric D sau L
-sensul rotatiei luminii polarizate () sau (-), determinat experimental
-dispunerea hidroxilului glicozidic (anomer u sau )
-numele ozei
-natura ciclului semiacetalic, piranozic sau Iuranozic.
C
C HO H
C OH H
C H
H
2
C
HO
CH
2
OH
O
OH
.D(-)-fructofuranoza
C
C OH H
C HO H
C OH H
C H
CH
2
OH
H
OH
O
-D(+)-glucopiranoza
omenclatura stereochimica
D()-glucoz: 2(R),(S),(R),(R),6-pentahidroxihexanal
D-(-)-Iructoza: (S),(R),(R),1,6-pentahidroxihexan-2-ona
!RO!RIETTI CHIMICE
a) Reac(ii datorate semiacetalizrii intramoleculare
- Mutarota(ia (in solutie apoasa)
-D-glucoza
.D-glucoza
[-]
D
=+112
o
[-]
D
=+18,7
o
rotatia speciIic la echilibru |u|
D
2,
o
Interconversia reversibil a celor doi anomeri n solutie
O
OH
OH
HO
HO
HOH
2
C
--D-glucopiranoza
O
OH
OH
HO
HO
HOH
2
C
.-D-glucopiranoza
O
OH
HO
HO
HOH
2
C
OH
O
OH
HO
HO
HOH
2
C
OH
H
H
n cataliz acid
O
H
OH
H
OH
H
OH H
OH
HOH
2
C
O
H
OH
OH
H
H
OH H
OH
CH
2
OH
--D-glucopiranoza
.-D-glucopiranoza
+ H
+
O
H
OH
H
OH
H
OH H
OH
HOH
2
C
H
OH
H
OH
O
H
OH H
OH
HOH
2
C
H
OH
H
OH
O
H
OH H
OH
HOH
2
C
H
-H
+
n cataliz bazic
O
H
OH
H
OH
H
OH H
OH
HOH
2
C
O
H
OH
OH
H
H
OH H
OH
CH
2
OH
--D-glucopiranoza
.-D-glucopiranoza
+ HO
-
O
H
OH
H
O
H
OH H
OH
HOH
2
C
O
H
OH
O
H
OH H
OH
HOH
2
C
H
OH
H
OH
O
H
OH H
OH
HOH
2
C
H
+H
2
O
-HO
-
a Reac(ii ale grupei carbonil
-reac(ii de reducere
C
C HO H
C OH H
C H
H
2
C
HO
CH
2
OH
O
OH
D-fructoza
C
C OH H
C HO H
C OH H
C H
CH
2
OH
H
OH
O
D-glucoza
C
C OH H
C HO H
C OH H
C H
CH
2
OH
H O
OH
Na/Hg
H
2
C
C OH H
C HO H
C OH H
C H
CH
2
OH
OH
OH
D-sorbitol
C
C HO H
C OH H
C H
H
2
C
O
CH
2
OH
OH
OH
C
C HO H
C OH H
C H
H
2
C
HO
CH
2
OH
OH
OH
H
D-manitol
H
2
C
C OH H
C HO H
C OH H
C H
CH
2
OH
OH
OH
D-sorbitol
+
Na/Hg
hexitoli
Condensarea cu compuyi cu azot
C
C OH H
C HO H
C OH H
C H
CH
2
OH
H O
OH
H
2
N-OH
C
C OH H
C HO H
C OH H
C H
CH
2
OH
H
N
OH
OH
-H
2
O
O
NH
OH
HO
HO
HOH
2
C
O
H
N
OH
HO
HO
HOH
2
C
OH
OH
+
oxima
-
.
C
C OH H
C HO H
C OH H
C H
CH
2
OH
H O
OH
H
2
N-HN-C
6
H
5
C
C OH H
C HO H
C OH H
C H
CH
2
OH
H
N
OH
NH
-H
2
O
C
6
H
5
fenilhidrazona glucozei
C
C
C HO H
C OH H
C H
CH
2
OH
H
N
OH
NH C
6
H
5
2H
2
N-HN-C
6
H
5
-C
6
H
5
-NH
2
-NH
3
-H
2
O
N NH C
6
H
5
osazona glucozei glucoza
C
C
C HO H
C OH H
C H
CH
2
OH
H
N
OH
NH C
6
H
5
N NH C
6
H
5
osazona glucozei
2H
2
O/H
+
-2C
6
H
5
NH-NH
2
C
C
C HO H
C OH H
C H
CH
2
OH
H O
OH
O
H
2
C
C
C HO H
C OH H
C H
CH
2
OH
OH
OH
O
osona fructoza
red.
a) Reac(ii de oxidare (57o57ietji 7educto7e).
Oxidarea blnd (acizi aldonici)
C
C OH H
C HO H
C OH H
C H
CH
2
OH
H O
OH
glucoza
HNO
3dil.
COOH
C OH H
C HO H
C OH H
C H
CH
2
OH
OH
acid gluconic
C=O
C OH H
C HO H
C H
C H
CH
2
OH
OH
O
-lactona
- H
2
O
+ H
2
O
Reactivi analitici:
reactivul Tollens,
reactivul Fehling
Oxidarea energica (acizi zaharici)
COOH
C OH H
C HO H
C OH H
C H
COOH
OH
acid glucozaharic
C=O
C OH H
C HO H
C H
C H
COOH
OH
O
1,4-lactona
- H
2
O
+ H
2
O
COOH
C OH H
C H
C OH H
C H
C=O
OH
O
3,6-lactona
+
- H
2
O
+ H
2
O
C=O
C OH H
C H
C H
C H
C=O
OH
O
O
1,4,3,6-dilactona
Oxidarea cu acid periodic
CHO
C H OH
C
CH
2
OH
H OH
eritroza
HO
4
3 HCOOH + H
2
C=O
CHO-CH(OH)
4
CH
2
OH + 5HO
4
CH
2
O + 5HCOOH + 5HO
3
tape de oxidare succesiv
CHO
C H OH
C
CH
2
OH
H OH
HO
4
+ HCOOH
CHO
C
CH
2
OH
H OH
HCOOH + H
2
C=O
etapa
etapa
CHO
C
CH
2
OH
H OH
HO
4
CHO
CH
2
OH
+ HCOOH
etapa
CHO
CH
2
OH
HO
4
Reac(ii ale hidroxilului glicozidic
Eterificarea
O
OH
OH
HO
HO
HOH
2
C
O
OH
OH
HO
HO
HOH
2
C
H
3
C-OH/HCl
(g)
H
3
C-OH/HCl
(g)
O
OCH
3
OH
HO
HO
HOH
2
C
O
OCH
3
OH
HO
HO
HOH
2
C
--D-glucopiranoza
--D-metilglucopiranozida
.-D-glucopiranoza
.-D-metilglucopiranozida
O
H
OH H
O
H
OH H
OH
CH
2
CH C
6
H
5
CN
O
H
OH H
O
H
OH H
OH
CH
2
OH
O
O
OH
HO
HO
HOH
2
C
H
3
CO
CHO
amigdalina
glucovanilina
licozide
O
OCH
3
OH
HO
HO
HOH
2
C
--D-metilglucopiranozida
H
3
C- / Ag
2
O
O
OCH
3
OCH
3
H
3
CO
H
3
CO
H
3
COH
2
C
pentametil---D-glucoza
Esterificarea
-esteri cu acizi organici
C
C OH H
C HO H
C OH H
C H
CH
2
OH
H O
OH
D-glucoza
O
OCO-CH
3
O
C
O
C
H
3
H
3
C-OCO
H
3
C-OCO
H
3
C-OCOH
2
C
--pentaacetil-D-glucoza
O
OCO-CH
3
O
C
O
C
H
3
H
3
C-OCO
H
3
C-OCO
H
3
C-OCOH
2
C
.-pentaacetil-D-glucoza
(H
3
C-CO)
2
O
ZnCl
2
0
o
H
3
C-COONa
(H
3
C-CO)
2
O
control
termodinamic
control
cinetic
-esteri cu acizi anorganici
Substitu(ia nucleofil
O
OAc
OAc
AcO
AcO
AcOH
2
C
.-D-pentaacetilglucoza
HBr
-CH
3
COOH
O
Br
OAc
AcO
AcO
AcOH
2
C
tetraacetatul --bromoglucozei
O
Br
OAc
AcO
AcO
AcOH
2
C
O
Cl
OAc
AcO
AcO
AcOH
2
C
O
O-C
6
H
5
OAc
AcO
AcO
AcOH
2
C
O
NH-R
OAc
AcO
AcO
AcOH
2
C
+ AgCl
+ C
6
H
5
O
-
K
+
+ R-NH
2
tetraacetatul-.-cloroglucozei
tetraacetatul-.-fenilglucozidei
tetraacetatul-.-aminoglucozidei
-AgBr
-KBr
-HBr
Acetalizarea
O
O
O
O
O
CH
2
OH
C
H
3
C
H
3
C
C
H
3
C CH
3
O
OH
OH
HO
HO
CH
2
OH
--D-galactoza
2 H
3
C-CO-CH
3
/ H
+
1,2,3,4-diizopropiliden-
--Dgalactopiranoza
-2H
2
O
Ac(iunea bazelor asupra ozelor
transpozitia Lobry de Bruyn-van ckenstein
D-glucoz a()
2
dil. 6, D-glucoz 2, D-manoz 1 D-Iructoz
CH=O
C H OH
aldoza
CH=O
C OH
CH=O
C HO
CH=O
C HO H
CH-O
C OH
CH
C O
OH CH
C O
OH
CH
2
C O
OH
aldoza
cetoza
-H
+
+H
+
+H
+
+H
+
-H
+
Ac(iunea acizilor asupra ozelor
CH
H
2
C
OH
CH
CH
CHO
OH HO
OH
H
+
-3H
2
O
O
CHO
furfurol
aldopentoza
HC
HC CH
CH
CHO
OH HO
H
+
-3H
2
O
O CHO
5-hidroximetilfurfurol aldohexoza
HO-H
2
C
HO-H
2
C
+H
2
O
COOH
CH
2
CH
2
C=O
CH
3
+ HCOOH
OH HO
acid levulic
Reac(ii de alungire a catenei monozaharidelor
Metoda Kiliani-Fischer
HC
O
C
C
H OH
H
2
C
H OH
OH
C H HO
D-arabinoza
HCN
CH HO
C
C
H OH
H
2
C
H OH
OH
C H HO
HC OH
C
C
H OH
H
2
C
H OH
OH
C H HO
CN
CN
+
cianhidrine epimere
H
2
O
-NH
3
CH HO
C
C
H OH
H
2
C
H OH
OH
C H HO
HC OH
C
C
H OH
H
2
C
H OH
OH
C H HO
COOH
COOH
+
acid gluconic acid manonic
CH HO
C
C
H OH
H
2
C
H OH
OH
C H HO
HC OH
C
C
H OH
H
2
C
H OH
OH
C H HO
COOH
COOH
-H
2
O
CH HO
C
C
H OH
H
2
C
H
OH
C H HO
CO
O
NaBH
4
CH HO
C
C
H OH
H
2
C
H OH
OH
C H HO
CHO
D-glucoza
HC OH
C
C
H OH
H
2
C
H
OH
C H HO
CO
O
-H
2
O
NaBH
4
HC OH
C
C
H OH
H
2
C
H OH
OH
C H HO
CHO
D-manoza
Reac(ii care duc la scurtarea catenei unei oze
Degradarea Ruff
HC
O
C
C
H OH
H
2
C
H OH
OH
C H HO
D-arabinoza
ox.
COOH
C
C
H OH
H
2
C
H OH
OH
C H HO
acid D-arabonic
H
2
O
2
, (H
3
C-COO)
3
Fe
- CO
2
- 2H
2
O
C
C
H OH
H
2
C
H OH
OH
HC
O
D-eritroza
Degradarea Wohl-Zemplen
HC O
C
C
H OH
H
2
C
H OH
OH
C H HO
D-arabinoza
HC O
C
C
H OH
H
2
C
H OH
OH
C H HO
C OH H
D-glucoza
H
2
N-OH
HC N-OH
C
C
H OH
H
2
C
H OH
OH
C H HO
C OH H
5(H
3
C-CO)
2
O
- 5H
3
C-COOH
- H
2
O
CN
C
C
H OAc
H
2
C
H OAc
OAc
C H AcO
C OAc H
CN
C
C
H OH
H
2
C
H OH
OH
C H HO
C OH H
-HCN
H
3
C-O
-
Na
+
-5AcOCH
3
oxima
nitril acetilat
cianhidrina

DIZAHARIDE
2 C
6
H
12
O
6
C
12
H
22
O
11
+ H
2
O
Determinarea structurii:
-identiIicarea ozelor componente,
-determinarea pozitiilor n care s-a realizat legtura dintre oze,
-determinarea naturii ciclurilor celor dou oze,
-determinarea conIiguratiei u sau glicozidice.
DIZAHARIDE REDUCTOARE
O
O
OH
HO
HO
HOH
2
C
4'---D-glucopiranozil)-.-D-glucopiranoza
O
OH
OH
HO
HOH
2
C
1'
2
3
4
5'
1
2'
3'
4'
5
semiacetal
anomer -
semiacetal
anomer .
O
O
OH
HO
HO
HOH
2
C
4'---D-glucopiranozil)-.-D-glucopiranoza
O
OH
OH
HO
HOH
2
C
O
O
OH
HO
HO
HOH
2
C
OH
O
HO
HOH
2
C
4'---D-glucopiranozil)-.-D-glucoza
Reprezentan(i
O
O
OH
HO
HO
HOH
2
C
4'---D-glucopiranozil)-.-D-glucopiranoza
maltoza
O
OH
OH
HO
HOH
2
C
1'
2
3
4
5'
1
2'
3'
4'
5
O
O
OH
HO
HO
HOH
2
C
4'-.-D-glucopiranozil)-.-D-glucopiranoza
celobioza
O
OH
OH
HO
HOH
2
C
1' 2
3
4
5'
1
2'
3'
4'
5
O
O
OH
HO
OH
4'-.-D-galactopiranozil)-D-glucopiranoza
lactoza
O
OH
OH
HO
HOH
2
C
1' 2
3
4
5'
1
2'
3'
4'
CH
2
OH
DIZRID RDUfTR
--D-glucopiranozil)---D-glucopiranozida
O
O
OH
HO
HO
HOH
2
C
O
OH
OH
HO
CH
2
OH 1
2
3
4
5
1
2
3
4
5
semiacetal
anomer -
semiacetal
anomer -
O
O
OH
HO
HO
2
3
4
1
CH
2
OH
O
OH
CH
2
OH
CH
2
OH
OH
1
2
3
4
5
6
--D-glucopiranozil-.-D-fructofuranozida
zaharoza
H
2
O/H
+
D-glucoza + D-fructoza
[-]
D
=+52,5
o
[-]
D
=-92,6
o
zaharoza
[-]
D
=+66,5
o
Invertirea zaharului |u|
D
20
o